JP5517452B2 - Production method of emulsion polymer - Google Patents

Abstract

The present invention provides a process for preparing emulsion polymer particles of a hollow core/shell structure in the presence of a monomer plasticizer having a ceiling temperature less than 181° C. wherein a polymerization inhibitor or reducing agent is not added to the aqueous emulsion of the core shell particles during the neutralization and swelling stage. The obtained core shell particles are useful in paints, paper coatings, foams, and cosmetics.

Description

  The present invention relates to a process for producing emulsion polymer particles having a core-shell structure and its use in paints, paper coatings, foams and cosmetics.

Organic hollow particles are a special kind of core-shell particles, which consist of air-filled cavities surrounded by a hard shell (Huelle) in a dry form. Based on this structure, the particles have the special property of scattering light, which provides evidence for their use as white pigments in paints, paper coatings, and in cosmetics such as Sonnencreme. . They are therefore used in place of the inorganic white pigment titanium dioxide and additionally enhance the effect of residual TiO ₂ .

  CJMcDonald and MJDevon, in Advances in Colloid and Interface Science 2002, 99, 181-213, have many possibilities for these hollow particles, for example, swelling with organic solvents or blowing agents, hydrocarbon encapsulation or W An approach based on an / O / W emulsion is described. However, a preferred method not only for natural environmental reasons but also for economic reasons is osmotic swelling of specific core-shell particles.

  EP 22633 describes this process as essential. In the first stage a hydrophilic core consisting of 15-70% of a polymerizable acid, for example acrylic acid or methacrylic acid, is produced, which is subsequently covered with a hard hydrophobic core consisting of nonionic monomers, for example styrene> 90% . After completion of the core-shell particle, it is expanded with ammonia or other volatile base at a temperature at or above the glass transition temperature of the envelope.

  EP 915108, EP 959176, EP 404184, US 5,360,827 and WO 00/68304 describe improvements in the above process. To facilitate expansion, the jacket is made soft by the addition of monomers or organic solvents, and after expansion has occurred, the plasticizer can be easily removed from the system by reaction consumption by the addition of radical initiators, or the system To remain. However, the use of monomers as plasticizers is associated with certain conditions. Based on their inherent reactivity, reactions must never be prevented from occurring earlier than expected, i.e. no significant reaction of the monomers should occur. As a measure for this, it is taught to wait for complete reaction consumption of the radical initiator, lowering of the expansion temperature and completion of addition of the polymerization inhibitor or reducing agent.

  However, this processing method is associated with several drawbacks. Not only must the cycle time extended by the waiting time be accepted, but it is also possible to fully utilize the plastic effect of the monomer and the resulting Tg reduction based on the lower expansion temperature required compared to conventional processes. Can not. However, the use of polymerization inhibitors has the most serious side effects. This is because they inevitably serve to reduce the final loss of the monomer. In some circumstances, this leads to the maximum concentration of monomer not reaching the desired point of expansion, but rather only when a further coat is applied that contributes to mechanical stability only afterwards, This weakens the jacket into an unstable one, and in the most disadvantageous case it can lead to its overall destruction by dissolution by plastic flow.

  The object of the present invention is therefore to develop a production process for emulsion polymer particles, in particular for organic hollow particles, which avoids the disadvantages of the prior art processes and has a high monomer concentration at the time of expansion. It was.

The problem is according to the invention
i) Seed (Saat)
ii) at least one nonionic ethylenically unsaturated monomer of 0 to 100% by weight and at least one monomer, based on the total weight of the Kernstufenpolymer each time as well as the seed and also including the expanded seed (Quellsaat) Expanded seeds containing 0-40% by weight of ethylenically unsaturated hydrophilic monomers iii) 85-99.9% by weight of at least one nonionic ethylenically unsaturated monomer and at least one hydrophilic monoethylenically unsaturated monomer A first shell containing 0.1 to 15% by weight iv) at least one nonionic ethylenically unsaturated monomer 85 to 99.9% by weight and at least one hydrophilic monoethylenically unsaturated monomer 0.1 A second shell containing ˜15% by weight v) Ceiling Tempera less than 181 ° C., preferably less than 95 ° C. at least one plasticizer monomer (Weichmachermonomer)
vi) neutralization of the particles so formed with a base to a pH value of at least 7.5 or preferably greater than 8;
vii) a third shell viii) containing 90-99.9% by weight of at least one nonionic ethylenically unsaturated monomer and 0.1-10% by weight of at least one hydrophilic monoethylenically unsaturated monomer; The emulsion optionally by the production of an aqueous emulsion comprising a multi-stage emulsion polymer containing a further shell containing at least one nonionic ethylenically unsaturated monomer and at least one hydrophilic monoethylenically unsaturated monomer It has been solved by a method of producing polymer particles.

  Yet another subject of the invention is the use of the emulsion polymers produced according to the invention in paints, paper coatings, foams and cosmetics.

  One advantage of the present invention is that in step (iv) the monomer whose ceiling temperature (Frieder Vieweg & Sohn Verlagsgesellschaft mbH, Braunschweig / Wiesbaden, 1997) is below the expansion temperature or, as an extreme case thereof, homogenous for thermodynamic reasons. If monomers that cannot form a polymer are used, the disadvantages of the prior art can be avoided and the swelling is possible even in the presence of the remaining amount of initiator without the addition of polymerization inhibitors or reducing agents. In the point.

  The described invention is a multi-stage continuous emulsion polymerization. Sequentially refers to the implementation of individual steps, where each individual step may consist of several consecutive steps.

  The concept of “seed” refers to an aqueous polymer dispersion that is used at the start of multi-stage polymerization and is the product from emulsion polymerization, or at the end of the polymerization stage to produce a hollow particle dispersion. It may refer to an aqueous polymer dispersion that is present except in stages.

  The seed used at the beginning of the first stage polymerization can also be prepared in situ and preferably consists of esters of acrylic acid, methacrylic acid, acrylic acid and methacrylic acid or mixtures thereof. Particularly preferred are mixtures from n-butyl acrylate, methyl methacrylate and methacrylic acid.

  The average particle size of the seed polymer is 40-100 nm, preferably 60-90 nm in the unexpanded state.

  The expanded seed comprises 0-100% by weight of nonionic ethylenically unsaturated monomer, preferably 55-80% by weight and monoethylenically unsaturated hydrophilic monomer 0-45% by weight, preferably 20-35% by weight. Containing.

  The mass ratio of expanded seed (ii) to seed polymer (i) is 2: 1 to 50: 1, preferably 2: 1 to 30: 1. The average particle size in the non-expanded state of the core stage polymer consisting of seed (i) and expanded seed (ii) is 100 to 400 nm, preferably 100 to 250 nm.

  The glass transition point of the core stage polymer, measured according to the Fox formula (John Wiley & Sons Ltd., Baffins Lane, Chichester, England, 1997) is between -20 ° C and 150 ° C.

Nonionic ethylenically unsaturated monomers are styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, _(C 1 ~C ₂₀₎ alkyl esters of acrylic or methacrylic acid or _(C 3 _{~C 20)} alkenyl esters, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, Oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl meta Relate, stearyl acrylate, stearyl methacrylate, monomers containing hydroxyl groups, in particular C ₁ -C 10 _- hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate , Ricinoleic acid, palmitooleic acid, oleic acid, elaidic acid, vaccenic acid, icosenic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, thymnodonic acid, iwasic acid.

  Monoethylenically unsaturated hydrophilic monomers include acrylic acid, methacrylic acid, acryloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, It is understood as monomethyl itaconate, maleic anhydride, fumaric acid, monomethyl fumarate, itaconic anhydride, itaconic acid monomethyl ester.

  The first shell (iii) comprises at least one nonionic ethylenically unsaturated monomer 85 to 99.9% by weight, preferably 90 to 99.9% by weight, and at least one hydrophilic monoethylenically unsaturated It contains 0.1 to 15% by weight of monomers, preferably 0.1 to 10% by weight.

Nonionic ethylenically unsaturated monomers are styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, _(C 1 ~C ₂₀₎ alkyl esters of acrylic or methacrylic acid or _(C 3 _{~C 20)} alkenyl esters, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, Oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl meta Relate, stearyl acrylate, stearyl methacrylate, monomers containing hydroxyl groups, in particular C ₁ -C 10 _- hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate , Ricinoleic acid, palmitooleic acid, oleic acid, elaidic acid, vaccenic acid, icosenic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, thymnodic acid, iwasic acid, preferably styrene Acrylonitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2- It is understood that hexyl methacrylate.

  Monoethylenically unsaturated hydrophilic monomers include acrylic acid, methacrylic acid, acryloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, Monomethyl itaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid monomethyl ester.

  The first shell (iii) includes a core stage polymer. The mass ratio of the core stage polymer to the first shell (iii) is 20: 1 to 1: 1, preferably 10: 1 to 1: 1, and the shell polymer is a Fox between −60 ° C. and 120 ° C. It has a glass transition point measured according to the formula:

  The particle size at this stage is 120 nm to 500 nm, preferably 150 to 270 nm in the unexpanded state.

  The second shell (iv) comprises at least one nonionic ethylenically unsaturated monomer 85 to 99.9% by weight, preferably 90 to 99.9% by weight and at least one hydrophilic monoethylenically unsaturated monomer 0.1 to 15% by weight, preferably 0.1 to 10% by weight.

Nonionic ethylenically unsaturated monomers are styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, _(C 1 ~C ₂₀₎ alkyl esters of acrylic or methacrylic acid or _(C 3 _{~C 20)} alkenyl esters, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, Oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl meta Relate, stearyl acrylate, stearyl methacrylate, monomers containing hydroxyl groups, in particular C ₁ -C 10 _- hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate , Ricinoleic acid, palmitooleic acid, oleic acid, elaidic acid, vaccenic acid, icosenic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, thymnodic acid, iwasic acid, preferably styrene Acrylonitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2- It is understood that hexyl methacrylate.

  Monoethylenically unsaturated hydrophilic monomers include acrylic acid, methacrylic acid, acryloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, Monomethyl itaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid monomethyl ester.

  The first shell is covered by a second shell and the mass ratio of the first shell (iii) to the second shell (iv) is 1:30 to 1: 1, preferably 1:20 to 1: 1 and the shell polymer has a glass transition point measured according to a Fox of 50-120 ° C. The average particle size at this stage is 200 nm to 1500 nm, preferably 250 to 600 nm.

  The plasticizer monomers described in (v) are, for example, α-methylstyrene, esters of 2-phenylacrylic acid / atropic acid (eg methyl, ethyl, n-propyl, n-butyl), 2-methyl-2- Butene, 2,3-dimethyl-2-butene, 1,1-diphenylethene or methyl-2-tert-butyl acrylate and other others described in J. Brandrup, EHImmergut, Polymer Handbook 3rd Edition, II / 316ff Understood as a monomer. Advantageously, α-methylstyrene is used as the plasticizer monomer.

  The neutralization described in (vi) is carried out using a base for expanding the core and thereby forming hollow particles. Bases such as alkali metal compounds or alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; ammonia; primary amines, secondary amines and tertiary amines, For example, ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropyl Amine, dimethylethanolamine, diisopropanolamine, morpholine, ethylenediamine, 2-diethylamineethylamine, 2,3-diaminopropane, 1,2-propylenediamine , Dimethylaminopropylamine, neopentanediamine, hexamethylenediamine, 4,9-oxa-1,12-diamine, polyethyleneimine or polyvinylamine can be used.

  The third shell (vii) comprises at least one nonionic ethylenically unsaturated monomer 90-99.9%, preferably 95-99.9% and at least one hydrophilic monoethylenically unsaturated monomer 0.1 to 10% by weight, preferably 0.1 to 5% by weight.

Nonionic ethylenically unsaturated monomers are styrene, vinyltoluene, ethylene, butadiene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, methacrylamide, _(C 1 ~C ₂₀₎ alkyl esters of acrylic or methacrylic acid or _(C 3 _{~C 20)} alkenyl esters, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, Oleyl acrylate, oleyl methacrylate, palmityl acrylate, palmityl meta Relate, stearyl acrylate, stearyl methacrylate, monomers containing hydroxyl groups, in particular C ₁ -C 10 _- hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate , Ricinoleic acid, palmitooleic acid, oleic acid, elaidic acid, vaccenic acid, icosenic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, thymnodic acid, iwasic acid, preferably styrene Acrylonitrile, methacrylamide, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2- It is understood that hexyl methacrylate.

  Monoethylenically unsaturated hydrophilic monomers include acrylic acid, methacrylic acid, acryloxypropionic acid, methacryloxypropionic acid, acryloxyacetic acid, methacryloxyacetic acid, crotonic acid, aconitic acid, itaconic acid, monomethyl maleate, maleic acid, Monomethyl itaconate, maleic anhydride, fumaric acid, monomethyl fumarate, preferably acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, itaconic acid monomethyl ester.

  The third shell also covers the second shell, and the mass ratio of the third shell to the second shell is 5: 1 to 1: 2, preferably 3: 1 to 1: 1, and the shell polymer Has a glass transition point according to a Fox of 50-120 ° C.

  When polymers prepared according to the invention are used for application (Anstrich), the final average particle size is desirably 300-800 nm, for paper and cosmetic applications 300-2500 nm, and For foam applications, it is desirable to be 300-800 nm.

Pigment used in the coating, in particular TiO ₂ can be replaced here by a completely or partially with the polymeric dispersion described. Typically such paints include water, thickeners, sodium hydroxide solutions, pigment dispersants, associative thickeners, foam suppressors, insecticides, binders, and film-forming aids (Filmbildenhilfsmittel). contains.

  Hollow particle dispersions may also be used for similar applications in resinous condensation products including phenolates and aminoplasts containing urea formaldehyde and melamine formaldehyde or other condensates such as water dispersible alkyds. Can be used.

Furthermore, the polymorphe heteropolymers of the described invention having a high proportion of large hollow particles and a relatively small proportion of small hollow particles are not only used as white pigments but also small hollow particles. Depending on the ratio, it may also have adhesive properties.
The use of pigments in the paper coating increases the gloss of the paper. This can be considered to be due to a plastic envelope under pressure, unlike in the case of inorganic pigments. Paper print quality is also improved. The exchange of inorganic pigments with the organic pigments described herein results in a reduced coating density and thereby a relatively light paper.

  In cosmetics, pigments can be used, for example, to enhance light protection in sunscreen creams. The outstanding light scattering properties increase the probability of absorbing UV radiation by the UV active substance in the sun cream.

  The polymer can be prepared according to conventional polymerization methods for emulsion polymers. It is preferably operated under exclusion of oxygen, preferably in a stream of nitrogen. For the polymerization process, the usual equipments are used, such as stirred tanks, stirred tank cascades, autoclaves, tubular reactors and kneaders. The polymerization is carried out using a solvent or diluent such as toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, industrial mixtures of alkylaromatic compounds, cyclohexane, industrial aliphatic mixtures, acetone, cyclohexanone, tetrahydrofuran, dioxane, It can be carried out in glycols and glycol derivatives, polyalkylene glycols and their derivatives, diethyl ether, t-butyl methyl ether, acetic acid methyl ester, isopropanol, ethanol, water or mixtures such as isopropanol / water mixtures.

  The polymerization can be carried out at a temperature of 20 to 300 ° C., preferably 50 to 200 ° C.

  The polymerization is preferably carried out in the presence of compounds that form radicals. Up to 30% by weight of these compounds, preferably 0.05 to 15% by weight, particularly preferably 0.2 to 8% by weight, based on the monomers used in the polymerization are required. In the case of a multi-component initiator system (eg a redox initiator system), the mass data is relative to the sum of the components.

  Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds. Examples for initiators that may be water soluble or water insoluble include hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, acetylacetone peroxide, t -Butyl hydroperoxide, cumene hydroperoxide, t-butyl perneodecanoate, t-amyl perpivalate, t-butyl perpivalate, t-butyl perneo hexanoate, t-butyl per-2-ethyl hexano Ate, t-butyl-perbenzoate, lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, azodiisobutyronitrile, 2,2′-azobis (2-amidinopropane) Dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4-azobis (4-cyanovaleric acid).

  The initiators can be used alone or mixed with one another, for example a mixture of hydrogen peroxide and sodium peroxodisulfate can be used. For polymerization in an aqueous medium, preferably a water-soluble initiator is used.

  Known redox initiator systems can also be used as polymerization initiators. Such a redox initiator system converts at least one peroxide-containing compound into a redox co-initiator, such as a sulfur compound having a reducing action, such as an alkali metal bisulfite, sulfite, thiosulfate, dithionite and Contains in combination with tetrathionate and ammonium compounds. Thus, a combination of peroxodisulfate and alkali metal bisulfite or ammonium bisulfite, such as ammonium peroxodisulfate and ammonium bisulfite can be used. The amount of peroxide-containing compound to redox coinitiator is 30: 1 to 0.05: 1.

  In combination with an initiator or redox initiator system, transition metal catalysts such as iron, cobalt, nickel, copper, vanadium and manganese salts can additionally be used. Suitable salts are, for example, iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride. The transition metal salt having a reducing action is used at a concentration of 0.1 ppm to 1000 ppm with respect to the monomer. Thus, a combination of hydrogen peroxide and iron (II) salt can be used, for example 0.5-30% hydrogen peroxide and 0.1-500 ppm molle salt.

  Upon polymerization in organic solvents, redox coinitiators and / or transition metal catalysts such as benzoin, dimethylaniline, ascorbic acid and heavy metals such as copper, cobalt, iron, manganese, nickel, in combination with the above initiators, A complex soluble in an organic solvent of chromium may be used in combination. The amount of redox coinitiator or transition metal catalyst normally used is usually about 0.1 to 1000 ppm, based on the amount of monomer used here.

  If the reaction mixture undergoes initial polymerization at the lower limit of the temperature range that is taken into account for polymerization and subsequently fully polymerizes at relatively high temperatures, it is possible to use at least two different initiators that decay at various temperatures. It is suitable for the purpose and results in a sufficient concentration of radicals in any temperature range.

  Initiators can be added during the stage, or the rate of initiator addition may vary outside the specification.

In order to produce a polymer with a low average molecular weight, it is often suitable for the purpose to carry out the copolymerization in the presence of a regulator. For this purpose, conventional regulators, for example compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, t-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan C ₁ -C ₄ -aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite, hypophosphorous acid or salts thereof or isopropanol can be used. The polymerization regulator is generally used in an amount of 0.1 to 20% by mass relative to the monomer. The selection of an appropriate solvent can also affect the average molecular weight. Thus, polymerization in the presence of a diluent having a benzylic H atom or in the presence of a secondary alcohol, such as isopropanol, results in a decrease in average molecular weight due to chain transfer.

  Polymers with low or relatively low molecular weight can also be obtained by changing temperature and / or initiator concentration and / or monomer feed rate.

  In order to produce relatively high molecular weight copolymers, it is often suitable for the purpose of operating in the presence of a crosslinking agent during the polymerization. Such crosslinkers are compounds having two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least divalent saturated alcohols such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene. Glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neo Pentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate. Acrylic esters and methacrylic esters of alcohols having more than two OH groups can also be used as crosslinkers, for example, trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Yet another class of crosslinkers are diacrylates or dimethacrylates of polyethylene glycol or polypropylene glycol each having a molecular weight of 200-9000. The polyethylene glycol or polypropylene glycol used for the production of diacrylate or dimethacrylate preferably has a molecular weight of 400 to 2000 each time. Besides the homopolymers of ethylene oxide or propylene oxide, block copolymers from ethylene oxide and propylene oxide or copolymers from ethylene oxide and propylene oxide can also be used, which contain randomly distributed ethylene oxide units and propylene oxide units. Ethylene oxide or propylene oxide oligomers are also used for the production of cross-linking agents such as diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate. Is suitable.

Further, as a cross-linking agent, vinyl acrylate, vinyl methacrylate, vinyl itaconate, adipic acid divinyl ester, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, allyl methacrylate, pentaerythritol triallyl ether, triallyl saccharose, pentaallyl Saccharose, pentaallyl sucrose, methylene bis (meth) acrylamide, divinylethylene urea, divinyl propylene urea, divinyl benzene, divinyl dioxane, triallyl cyanurate, tetraallyl silane, tetravinyl silane and bis- or polyacryl siloxanes (eg Th. Goldschmidt AG Tegomer ^(R) ) is suitable.

  The crosslinking agent is preferably used in an amount of 0.1 to 30% by weight, based on the monomer to be polymerized or the monomer to be polymerized in one step. The crosslinking agent may be added at any stage.

  Furthermore, it may be advantageous to stabilize the polymer droplets or polymer particles with a surfactant. Typically emulsifiers or protective colloids are used for this purpose. Anionic, nonionic, cationic and amphoteric emulsifiers are taken into account. Anionic emulsifiers are, for example, alkylbenzene sulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. As nonionic emulsifiers, for example, alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO-block copolymers and alkylpolyglucosides can be used. As cationic or amphoteric emulsifiers, for example, quaternized amine alkoxylates, alkylbetaines, alkylamidobetaines and sulfobetaines are used.

  Typical protective colloids are, for example, cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene oxide and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ether, starch and starch derivatives, dextran, polyvinyl pyrrolidone, polyvinyl pyridine, polyethylene imine. , Polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolidone-2, polyvinyl-2-methylimidazoline and maleic acid or maleic anhydride copolymer, for example they are DE2501123 It is described in.

  Usually, the emulsifier or protective colloid is used in a concentration of 0.05 to 20% by weight with respect to the monomer.

  When polymerized in aqueous or dilute solution, the monomers can be wholly or partially neutralized with base before or during polymerization. Bases such as alkali metal compounds or alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; ammonia; primary amines, secondary amines and tertiary amines, For example, ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropyl Amine, dimethylethanolamine, diisopropanolamine or morpholine are considered.

  Polybasic amines can also be used for neutralization, such as ethylenediamine, 2-diethylamineethylamine, 2,3-diaminopropane, 1,2-propylenediamine, dimethylaminopropylamine, neopentanediamine, hexamethylenediamine, 4 , 9-Dioxadodecane-1,12-diamine, polyethyleneimine or polyvinylamine can be used.

  Advantageously, ammonia, triethanolamine and diethanolamine are used for partial or complete neutralization of the ethylenically unsaturated carboxylic acid before or during the polymerization.

  Particularly advantageously, the ethylenically unsaturated carboxylic acid is not neutralized before and during the polymerization. The polymerization can be carried out continuously or discontinuously according to a number of variants. Usually, some of the monomers are charged, deactivated, and in the desired polymerization temperature, optionally in a suitable diluent or solvent and optionally in the presence of emulsifiers, protective colloids or further auxiliaries. The temperature is increased until However, only suitable diluents may be charged. Within a defined time, the radical initiator in the diluent, as well as other monomers and other auxiliaries, such as regulators or crosslinkers, are metered in each case. The supply time may be selected for different lengths. For example, a longer feed time for monomer feed may be selected for the initiator feed.

  If the polymer is produced in a vapor volatile solvent or solvent mixture, the solvent can be separated by vapor conduction, thus obtaining an aqueous solution or dispersion. The polymer can also be separated from the organic diluent by a drying process.

Experimental Method Measurement of Glass Transition Point The glass transition point was measured by theoretical calculation using the Fox equation (John Wiley & Sons Ltd., Baffins Lane, Chichester, England, 1997).

1 / Tg = W _a / T _ga + W _b / T _gb ,
[ _Wherein T _ga and T _gb = the glass transition temperatures W _a and W _{b of the} polymers “a” and “b” = mass proportions of the polymers “a” and “b”].

Particle size measurement Particle size measurement is also known as quasi-photoelastic light scattering or dynamic light scattering by Coulter M4 + (particle analyzer) or using Malvern HPPS (High Performance Particle Sizer). (ISO 13321-standard) by photon correlation spectroscopy or by hydrodynamic fractionation (Hydrodynamische Fraktionierung) using Polymer Labs PSDA (particle size distribution analyzer).

Measurement of whiteness measurement 6 g of the following colored paste (Farbpaste) and 1 g of a hollow particle dispersion of about 30% were weighed into a container and the mixture was homogenized-without the introduction of air. A film of this mixture was placed on a black plastic sheet (matte finish, Article No. 13.41 EG 870934001, Bernd Schwegmann GmbH & Co. KG, D) at a rate of 0.9 cm / sec using a 200 μm doctor blade. Enlarged. The sample was dried at 23 ° C. and 40-50% relative humidity for 24 hours. Subsequently, the whiteness of three different locations is measured using a spectrophotometer with the registered trademark “Minolta CM-508i”. The measurement points are marked for later measurement using a micrometer screw to measure the corresponding layer thickness of the colored sheet by differential measurement on an uncoated plastic sheet. After calculating the average layer thickness from the three individual measurements as well as the average whiteness, the resulting whiteness is finally determined by lineare extrapolation for a dry layer thickness of 50 μm. Standardized. The calibration required for this was performed by measuring the whiteness of the standard hollow particle dispersion in a region having a dry layer thickness of about 30 to 60 μm.

EXAMPLE Preparation of a colored paste A) 240 g of water are charged into a container, after which the following substances used are added in the order described using a dissolver operating at about 1000 rpm and homogeneous for a total of about 15 minutes: Stir until
Natrosol ^(R) 250 HR (Hercules GmbH, Hydroxyethylcellulose-Thickener) 2.5 g, 1 g of 10% sodium hydroxide solution, Pigmentverteiler ^(R) MD 20 (BASF AG from maleic acid and diisobutylene) ^{copolymer) 6g, Collacral (R) LR} 8990 (BASF AG Corporation polyurethane - associative ^{thickener) 10g, Agitan (R) E} 255 (Muenzing Chemie GmbH Co. siloxane foam ^{inhibitor) 3g, Proxel (R) BD} 20 (Avecia Inc Co. ^{pesticides) 2g, Acronal (R) a} 684 ( binder, BASF AG Corporation 50% of the ^{dispersion) 370g, Taxanol (R) (} Eastman Chemical Com any company auxiliary film-forming ^{agent) 20g, Agitan (R) E} 255 (Muenzing Chemie GmbH Co. siloxane foam inhibitor) 2 g, 5% of Collacral LR 8989 (BASF AG polyurethane-associative thickener) 10 g.

B) Charge 250 g of water into the vessel, then add the following materials in the order listed using a dissolver operating at about 1000 rpm and stir for a total of about 15 minutes until homogeneous :
Natrosol ^(R) 250 HR (Hercules GmbH, Hydroxyethylcellulose-Thickener) 2.5 g, 1 g of 10% sodium hydroxide solution, Pigmentverteiler ^(R) MD 20 (BASF AG from maleic acid and diisobutylene) ^{copolymer) 6g, Collacral (R) LR} 8990 (BASF AG Corporation polyurethane - associative ^{thickener) 10g, Agitan (R) E} 255 (Muenzing Chemie GmbH Co. siloxane foam ^{inhibitor) 3g, Proxel (R) BD} 20 (Avecia Inc Co. ^{pesticides) 2g, Kronos 2300 203g, Acronal} (R) a 684 ( binder, BASF AG Corporation 50% of the ^{dispersion) 370g, Taxanol (R) (} Eas man Chemical Company Inc. of film-forming ^{aid) 20g, Agitan (R) E} 255 (Muenzing Chemie GmbH Co. siloxane foam inhibitor) 2 g, 5% of Collacral LR 8989 (BASF AG polyurethane-associative thickener) 10 g, hollow particle dispersion 116 g.

Dispersion A (seed)
A pre-emulsion was prepared from 230 g water, 2.17 g aryl sulfonate (15%), 338 g n-butyl acrylate, 303.6 g methyl methacrylate and 8.45 g methacrylic acid. A charge consisting of 2356 g of water, 32.0 g of aryl sulfonate (15%) and 41.2 g of pre-emulsion was placed in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels at 80 ° C. in a nitrogen atmosphere. The initial polymerization was carried out for 15 minutes after heating to temperature and addition of 14 g of a solution of 22.4% ammonium persulfate. The remainder of the pre-emulsion was then metered in at 80 ° C. within 60 minutes. It was subsequently postpolymerized for a further 15 minutes and cooled to 55 ° C. within 20 minutes. In order to deplete the residual monomer, 6.5 g of a 10% solution of t-butyl hydroperoxide as well as 8.1 g of a 5% Rongalit C solution are then added to the reaction mixture and, after cooling to 30 ° C., 25% of ammonia. The pH value of the dispersion was adjusted by adding 8.1 g of the solution.
Solid content: 19.7%
pH value: 2.6
Particle size (AUZ, D50): 47 nm

Dispersion B1 (expanded core)
A charge consisting of 1455 g of water and 63.2 g of dispersion A was heated to a temperature of 79 ° C. in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels, to a temperature of 79 ° C. and 2.5 Initial polymerization occurred for 5 minutes after the addition of 10 g of a solution of% sodium persulfate. Then within 113 minutes pre-emulsion 1 consisting of 262 g water, 3.33 g aryl sulfonate (15%), 20.75 g Lutensit A-EP (acid form, 20%), 186.6 g methyl methacrylate and 124.4 g methacrylic acid Was metered in at 79 ° C. This was followed by pre-emulsion 2 consisting of 254 g of water, 2.67 g of aryl sulfonate (15%), 187 g of methyl methacrylate and 2.05 g of methacrylic acid, together with 22 g of 2.5% sodium persulfate solution within 67 minutes. Weighed in at ° C. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.9%
pH value: 2.5
Particle size (Autosizer): 195 nm

Dispersion B2 (expanded core)
A charge consisting of 1455 g of water and 42.0 g of dispersion A is heated to a temperature of 79 ° C. in a nitrogen atmosphere in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels, and 2.5 Initial polymerization occurred for 5 minutes after the addition of 10 g of a solution of% sodium persulfate. Next, pre-emulsion 1 consisting of 262 g of water, 3.33 g of aryl sulfonate (15%), 20.75 g of Lutensit A-EP (acid form, 20%), 211.8 g of methyl methacrylate and 104.3 g of methacrylic acid within 113 minutes Was metered in at 79 ° C. This was followed by pre-emulsion 2 consisting of 254 g of water, 2.67 g of aryl sulfonate (15%), 186 g of methyl methacrylate and 2.05 g of methacrylic acid within 67 minutes together with 22 g of 2.5% sodium persulfate solution. Weighed in at ° C. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.7%
pH value: 2.9
Particle size (Autosizer): 211 nm

Dispersion B3 (expanded core)
A charge consisting of 1009 g of water and 28.7 g of Acronal A 508 was heated to a temperature of 82 ° C. in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels and a temperature of 2.5 ° C. Initial polymerization occurred for 5 minutes after the addition of 20.2 g of a solution of% sodium persulfate. Then from 163 g of water, 2.24 g of aryl sulfonate (15%), 13.95 g of Lutensit A-EPA (partially neutralized, 20%), 124.9 g of methyl methacrylate and 83.6 g of methacrylic acid and 0.50 g of allyl methacrylate The resulting pre-emulsion 1 was metered in at 82 ° C. within 70 minutes. Around the end of the feed, 3.0 g of a 2.5% sodium persulfate solution was added and stirred for 5 minutes. This was followed by pre-emulsion 2 consisting of 171 g of water, 1.79 g of aryl sulfonate (15%), 112 g of methyl methacrylate, 13.8 g of n-butyl acrylate and 1.38 g of methacrylic acid, 12 g of a 2.5% sodium persulfate solution. Was metered in at 82 ° C. within 70 minutes. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.8%
pH value: 4.4
Particle size (Autosizer): 207nm

Dispersion B4 (expanded core)
1. Charge a charge consisting of 1542 g of water and 44.2 g of dispersion A in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and Initial polymerization occurred for 5 minutes after the addition of 10.6 g of a 5% sodium persulfate solution. Then, pre-emulsion 1 consisting of 277 g of water, 3.53 g of aryl sulfonate (15%), 22.00 g of Lutensit A-EP (acid form, 20%), 222.6 g of methyl methacrylate and 109.7 g of methacrylic acid is within 113 minutes. The polymerization temperature was continuously lowered from 82 ° C to 80 ° C. This was followed by pre-emulsion 2 consisting of 269 g of water, 2.83 g of aryl sulfonate (15%), 196 g of methyl methacrylate and 2.17 g of methacrylic acid within 80 minutes with 23 g of 2.5% sodium persulfate solution. Weighed in at ° C. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.7%
pH value: 2.7
Particle size (Autosizer): 215 nm

Dispersion B5 (expanded core)
A charge consisting of 1009 g of water and 28.7 g of Acronal A 508 was heated to a temperature of 82 ° C. in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels and a temperature of 2.5 ° C. Initial polymerization occurred for 5 minutes after the addition of 20.2 g of a solution of% sodium persulfate. Then from 163 g of water, 2.24 g of aryl sulfonate (15%), 13.95 g of Lutensit A-EPA (partially neutralized, 20%), 125.0 g of methyl methacrylate, 83.6 g of methacrylic acid and 0.34 g of allyl methacrylate. The resulting pre-emulsion 1 was metered in at 82 ° C. within 70 minutes. Around the end of the feed, 3.0 g of a 2.5% sodium persulfate solution was added and stirred for 5 minutes. This was followed by pre-emulsion 2 consisting of 171 g of water, 1.79 g of aryl sulfonate (15%), 112 g of methyl methacrylate, 13.8 g of n-butyl acrylate and 1.38 g of methacrylic acid, 12 g of a 2.5% sodium persulfate solution. Was metered in at 82 ° C. within 70 minutes. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.8%
pH value: 4.4
Particle size (Autosizer): 220 nm

Dispersion B6 (expanded core)
A charge consisting of 1613 g of water and 45.2 g of Acronal A 508 was heated to a temperature of 82 ° C. in a nitrogen atmosphere in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels, and 2.5 Initial polymerization occurred for 5 minutes after the addition of 10.6 g of a solution of% sodium persulfate. Then 70 g of pre-emulsion 1 consisting of 127 g of water, 1.77 g of aryl sulfonate (15%), 11.13 g of Lutensit A-EPA (partially neutralized, 20%), 99.1 g of methyl methacrylate and 65.7 g of methacrylic acid. Metered at 82 ° C. within minutes. Simultaneously from 127 g water, 1.77 g aryl sulfonate (15%), 11.13 g Lutensit A-EPA (partially neutralized, 20%), 110.1 g methyl methacrylate, 54.2 g methacrylic acid and 0.53 g allyl methacrylate The resulting pre-emulsion 2 was metered into pre-emulsion 1 within 70 minutes (Power-Feed-Fahrweise). Around the end of the feed, 4.7 g of a 2.5% sodium persulfate solution was added and stirred for 5 minutes. This was followed by pre-emulsion 3 consisting of 269 g water, 2.83 g aryl sulfonate (15%), 176 g methyl methacrylate, 21.7 g n-butyl acrylate and 2.17 g methacrylic acid, 19 g of a 2.5% sodium persulfate solution. Was metered in at 82 ° C. within 70 minutes. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.8%
pH value: 4.3
Particle size (Autosizer): 210 nm

Dispersion B7 (expanded core)
A charge consisting of 1589 g of water and 45.2 g of Acronal A 508 was heated in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and 2.5 Initial polymerization occurred for 5 minutes after the addition of 10.6 g of a solution of% sodium persulfate. Then from 277 g water, 3.53 g aryl sulfonate (15%), 22.00 g Lutensit A-EPA (partially neutralized, 20%), 222.1 g methyl methacrylate, 0.53 g allyl methacrylate and 109.7 g methacrylic acid. The resulting pre-emulsion 1 was metered in at 82 ° C. within 70 minutes. Around the end of the feed, 4.7 g of a 2.5% sodium persulfate solution was added and stirred for 5 minutes. This was followed by pre-emulsion 2 consisting of 269 g of water, 2.83 g of aryl sulfonate (15%), 196 g of methyl methacrylate and 2.17 g of methacrylic acid within 70 minutes together with 23 g of a 2.5% sodium persulfate solution. Weighed in at ° C. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.7%
pH value: 4.8
Particle size (Autosizer): 209 nm

Dispersion B8 (expanded core)
A charge consisting of 986 g of water and 28.2 g of Acronal A 508 was heated to a temperature of 82 ° C. in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels and a temperature of 2.5 ° C. Initial polymerization occurred for 5 minutes after addition of 20.9 g of a solution of% sodium persulfate. Then 161 g of water, 2.20 g of aryl sulfonate (15%), 13.70 g of Lutensit A-EPA (partially neutralized, 20%), 0.07 g of t-dodecyl mercaptan, 136.3 g of methyl methacrylate, 0. 3 g of allyl methacrylate. Pre-emulsion 1 consisting of 66 g and 68.3 g of methacrylic acid was metered in at 82 ° C. within 70 minutes. At the end of the feed, 2.9 g of a 2.5% sodium persulfate solution was added and stirred for 5 minutes. This was followed by 167 g of water, 1.76 g of aryl sulfonate (15%), 110 g of methyl methacrylate, 13.5 g of n-butyl acrylate and 1.35 g of methacrylic acid, and 12 g of a 2.5% sodium persulfate solution. Was metered in at 82 ° C. within 70 minutes. Finally, postpolymerization was conducted for another 30 minutes.
Solid content: 19.7%
pH value: 4.3
Particle size (Autosizer): 213 nm

Comparative test:
Dispersion C1
1. Charge a charge consisting of 513 g of water and 158.3 g of dispersion B1 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 80 ° C. in a nitrogen atmosphere and Initial polymerization occurred for 5 minutes after the addition of 14.4 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 158 g of water, 6.6 g of aryl sulfonate (15%), 11.3 g of methacrylic acid and 180 g of styrene was then added within 80 minutes together with 18.3 g of a 2.5% sodium persulfate solution. At the start, metering was carried out at 80 ° C., at the end of the feed the internal temperature was increased to 92 ° C. and the supply of sodium persulfate was stopped. After the emulsion feed is complete, add pre-emulsion 2 consisting of 16 g of water, 0.6 g of aryl sulfonate (15%) and 15.8 g of α-methylstyrene and stir for 5 minutes, then 30 g of 10% ammonia in water. The reaction mixture was stirred at 92 ° C. for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 210 g of water, 7.5 g of aryl sulfonate (15%), 22.5 g of methyl methacrylate and 221 g of styrene was added to 92 ° C. within 100 minutes together with 27.4 g of a 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 13.5 g of a 10% t-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.9%
pH value: 7.6

Dispersion C1V
The synthesis was carried out in the same way as the preparation of dispersion C1, with the difference that pre-emulsion 2 contains the same amount of methyl methacrylate instead of α-methylstyrene.
Solid content: 29.5%
pH value: 8.8

Dispersion C2V
The synthesis was carried out in the same way as the preparation of dispersion C1, with the difference that pre-emulsion 2 contains the same amount of styrene instead of α-methylstyrene.
Solid content: 29.5%
pH value: 8.9

Dispersion C3V
Synthesis as in the preparation of dispersion C1, except that pre-emulsion 2 is replaced with α-methylstyrene in the same amount of styrene and additionally Irganox HP 2215 (Ciba Specialty Chemicals Inhibitor) 0.45 g With the difference of containing.
Solid content: 29.2%
pH value: 8.5

  As can be easily read from the table above, only C1 behaves ideally and has a much higher whiteness. C1 shows the ideal behavior of the residual monomer during the expansion process, ie the maximum at the time of ammonia addition where no significant reduction occurs, as well as a clear decrease after the addition of pre-emulsion 3 (VE3). In contrast to the ideal behavior just described, methyl methacrylate and styrene as swelling monomers decompose very quickly (CV1 + CV2) and the addition of inhibitors cannot prevent this (CV3). Rather, the inhibitor has a destructive effect on subsequent further polymerization after the addition of pre-emulsion 3. Control of the expansion technique also appears in the behavior of increasing particle size. Only in the case of C1 a major expansion occurs at the desired time, i.e. immediately after pH adjustment. In other cases, the particles will also clearly grow during the polymerization of the stabilizing skin, which may result in worse whiteness.

Yet another hollow particle-dispersion according to the invention:
Dispersion C2a:
1. A charge consisting of 501 g of water and 152.0 g of dispersion B2 is heated to a temperature of 80 ° C. in a nitrogen atmosphere in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two supply vessels; Initial polymerization occurred for 5 minutes after the addition of 14.4 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 158 g of water, 6.6 g of aryl sulfonate (15%), 9.7 g of methacrylic acid and 155 g of styrene was then added within 80 minutes together with 16.7 g of a 2.5% sodium persulfate solution. At the start, metering was carried out at 80 ° C., at the end of the feed the internal temperature was increased to 92 ° C. and the supply of sodium persulfate was stopped. After the emulsion feed is complete, 16 g of water, 0.6 g of aryl sulfonate (15%) and 13.5 g of α-methylstyrene are added and stirred for 5 minutes, then 26 g of 10% ammonia water The reaction mixture was stirred at 92 ° C. for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 229 g of water, 7.5 g of aryl sulfonate (15%), 25.2 g of methyl methacrylate and 247 g of styrene was added to 92 ° C. within 100 minutes together with 29.0 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 13.5 g of a 10% t-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 28.5%
pH value: 8.7
Particle size (Autosizer): 731 nm (polydispersity 0.13)
Whiteness: 74

Dispersion C2b:
1. Charge a charge consisting of 486 g of water and 174.7 g of Dispersion B2 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 80 ° C. in a nitrogen atmosphere and Initial polymerization occurred for 5 minutes after the addition of 14.4 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 179 g of water, 7.5 g of aryl sulfonate (15%), 11.0 g of methacrylic acid and 176 g of styrene was then added within 90 minutes together with 18.9 g of a 2.5% sodium persulfate solution. At the start, metering was carried out at 80 ° C., at the end of the feed the internal temperature was increased to 92 ° C. and the supply of sodium persulfate was stopped. After the emulsion feed is complete, add pre-emulsion 2 consisting of 16 g water, 0.6 g aryl sulfonate (15%) and 15.3 g α-methylstyrene and stir for 5 minutes, then 29 g of 10% ammonia in water The reaction mixture was stirred at 92 ° C. for an additional 15 minutes. Subsequently, 4.0 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 207 g of water, 6.6 g of aryl sulfonate (15%), 22.7 g of methyl methacrylate and 225 g of styrene was added to 92 ° C. within 90 minutes together with 26.7 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 13.5 g of a 10% t-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.3%
pH value: 8.7
Particle size (Autosizer): 719 nm (PD 0.18)
Whiteness: 70

Dispersion C3:
1. Charge a charge consisting of 486 g of water and 181.2 g of dispersion B3 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and Initial polymerization occurred for 5 minutes after the addition of 14.4 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 179 g of water, 7.5 g of aryl sulfonate (15%), 11.0 g of methacrylic acid and 176 g of styrene was then added within 90 minutes together with 18.9 g of a 2.5% sodium persulfate solution. Metered at 82 ° C. After finishing both feeds, the internal temperature was raised to 92 ° C. within 30 minutes, then pre-emulsion 2 consisting of 16 g of water, 0.6 g of aryl sulfonate (15%) and 15.3 g of α-methylstyrene was added and Stirring for 5 minutes was followed by the addition of 29 g of 10% ammonia in water; the reaction mixture was stirred for an additional 15 minutes at 92 ° C. Subsequently, 4.0 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3, consisting of 177 g of water, 6.6 g of aryl sulfonate (15%), 22.7 g of methyl methacrylate and 223 g of styrene, was added at 92 ° C. within 115 minutes together with 26.7 g of a 2.5% sodium persulfate solution. Weighed in. After 55 minutes feeding time, 32.1 g of 7% itaconic acid was added to Pre-Emulsion 3. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 13.5 g of a 10% t-butyl hydroperoxide solution and 13.5 g of a 10% ascorbic acid solution were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.1%
pH value: 7.0
Particle size (Autosizer): 519 nm (PD 0.09)
Whiteness: 73

Dispersion C4:
1. Charge a charge consisting of 431 g of water and 155.3 g of dispersion B4 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 80 ° C. in a nitrogen atmosphere and Initial polymerization was carried out for 5 minutes after the addition of 12.8 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 159 g of water, 6.7 g of aryl sulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene is then added within 90 minutes together with 16.8 g of a 2.5% sodium persulfate solution. At the start, metering was carried out at 80 ° C., at the end of the feed the internal temperature was increased to 92 ° C. and the supply of sodium persulfate was stopped. After the emulsion feed is complete, add pre-emulsion 2 consisting of 14 g water, 0.5 g aryl sulfonate (15%) and 13.6 g α-methylstyrene and stir for 5 minutes, then 26 g 10% ammonia water The reaction mixture was stirred at 92 ° C. for an additional 15 minutes. Subsequently, 3.6 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 158 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene was combined with 23.7 g of a 2.5% sodium persulfate solution within 90 minutes at 92 ° C. Weighed in. After a feed time of 45 minutes, 28.6 g of 7% itaconic acid was added to Pre-Emulsion 3. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 12.0 g of a 10% solution of t-butyl hydroperoxide as well as 12.0 g of a 10% solution of ascorbic acid were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 28.8%
pH value: 8.0
Particle size (Autosizer): Unmeasurable whiteness: 72

Dispersion C5:
1. Charge a charge consisting of 458 g of water and 154.5 g of dispersion B5 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and Initial polymerization was carried out for 5 minutes after the addition of 12.8 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 159 g of water, 6.7 g of aryl sulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene is then added within 90 minutes together with 16.8 g of a 2.5% sodium persulfate solution. Metered at 82 ° C. After finishing both feeds, the internal temperature was raised to 92 ° C. within 30 minutes, then pre-emulsion 2 consisting of 14 g of water, 0.5 g of aryl sulfonate (15%) and 13.6 g of α-methylstyrene was added and Stirring for 5 minutes followed by the addition of 26 g of 10% ammonia in water; the reaction mixture was stirred for an additional 15 minutes at 92 ° C. Subsequently, 3.6 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 157 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene was added to 92 ° C. within 100 minutes together with 23.7 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 12.0 g of a 10% solution of t-butyl hydroperoxide as well as 12.0 g of a 10% solution of ascorbic acid were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 28.9%
pH value: 8.3
Particle size (Autosizer): 571 nm (PD 0.06)
Whiteness: 78

Dispersion C6:
1. A charge consisting of 458 g of water and 154.5 g of dispersion B6 is heated to a temperature of 82 ° C. in a nitrogen atmosphere in a polymerization vessel equipped with a horseshoe stirrer, a reflux condenser and two feed vessels; Initial polymerization was carried out for 5 minutes after the addition of 12.8 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 159 g of water, 6.7 g of aryl sulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene is then added within 90 minutes together with 16.8 g of a 2.5% sodium persulfate solution. Metered at 82 ° C. After finishing both feeds, the internal temperature was raised to 92 ° C. within 30 minutes, then pre-emulsion 2 consisting of 14 g of water, 0.5 g of aryl sulfonate (15%) and 13.6 g of α-methylstyrene was added and Stirring for 5 minutes followed by the addition of 26 g of 10% ammonia in water; the reaction mixture was stirred for an additional 15 minutes at 92 ° C. Subsequently, 3.6 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 157 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene was added to 92 ° C. within 100 minutes together with 23.7 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 12.0 g of a 10% solution of t-butyl hydroperoxide as well as 12.0 g of a 10% solution of ascorbic acid were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.4%
pH value: 8.8
Particle size (Autosizer): 560 nm (PD 0.11)
Whiteness: 77

Dispersion C7:
1. Charge a charge consisting of 458 g of water and 155.3 g of Dispersion B7 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and Initial polymerization was carried out for 5 minutes after the addition of 12.8 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 159 g of water, 6.7 g of aryl sulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene is then added within 90 minutes together with 16.8 g of a 2.5% sodium persulfate solution. Metered at 82 ° C. After finishing both feeds, the internal temperature was raised to 92 ° C. within 30 minutes, then pre-emulsion 2 consisting of 14 g of water, 0.5 g of aryl sulfonate (15%) and 13.6 g of α-methylstyrene was added and Stirring for 5 minutes followed by the addition of 26 g of 10% ammonia in water; the reaction mixture was stirred for an additional 15 minutes at 92 ° C. Subsequently, 3.6 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 157 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene was added to 92 ° C. within 100 minutes together with 23.7 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 12.0 g of a 10% solution of t-butyl hydroperoxide as well as 12.0 g of a 10% solution of ascorbic acid were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.4%
pH value: 8.8
Particle size (Autosizer): 578 nm (PD 0.08)
Whiteness: 77

Dispersion C8:
1. Charge a charge consisting of 458 g of water and 154.5 g of dispersion B8 in a polymerization vessel equipped with a horseshoe stirrer, reflux condenser and two feed vessels to a temperature of 82 ° C. in a nitrogen atmosphere and Initial polymerization was carried out for 5 minutes after the addition of 12.8 g of a 5% sodium persulfate solution. A pre-emulsion 1 consisting of 159 g of water, 6.7 g of aryl sulfonate (15%), 9.8 g of methacrylic acid and 156 g of styrene is then added within 90 minutes together with 16.8 g of a 2.5% sodium persulfate solution. Metered at 82 ° C. After finishing both feeds, the internal temperature was raised to 92 ° C. within 30 minutes, then pre-emulsion 2 consisting of 14 g of water, 0.5 g of aryl sulfonate (15%) and 13.6 g of α-methylstyrene was added and Stirring for 5 minutes followed by the addition of 26 g of 10% ammonia in water; the reaction mixture was stirred for an additional 15 minutes at 92 ° C. Subsequently, 3.6 g of a 2.5% sodium persulfate solution was metered in within 3 minutes. Pre-emulsion 3 consisting of 157 g of water, 5.9 g of aryl sulfonate (15%), 20.2 g of methyl methacrylate and 198 g of styrene was added to 92 ° C. within 100 minutes together with 23.7 g of 2.5% sodium persulfate solution. Weighed in. Finally, postpolymerization was conducted for another 30 minutes. Further chemical deodorization was finally performed to reduce residual monomer. For this purpose, 12.0 g of a 10% solution of t-butyl hydroperoxide as well as 12.0 g of a 10% solution of ascorbic acid were metered into the reaction mixture at 92 ° C. within 60 minutes in parallel.
Solid content: 29.3%
pH value: 8.6
Particle size (Autosizer): 544 nm (PD 0.13)
Whiteness: 76

Claims (19)

A process for producing emulsion polymer particles by the production of a multi-stage emulsion polymer comprising the following continuous polymerization:
i) polymerizing the seed, followed by ii) 0-100% by weight of at least one nonionic ethylenically unsaturated monomer, based on the total weight of the core stage polymer containing seed (i) and expanded seed (ii) And an expanded seed containing 0-40% by weight of at least one monoethylenically unsaturated hydrophilic monomer, followed by iii) 85-99.9% by weight of at least one nonionic ethylenically unsaturated monomer Polymerized with a first shell containing 0.1-15% by weight of at least one hydrophilic monoethylenically unsaturated monomer and subsequently iv) at least one nonionic ethylenically unsaturated monomer 85-99.9% And a second shell containing at least one hydrophilic monoethylenically unsaturated monomer from 0.1 to 15% by weight. Continued v) at least one plasticizer monomer having a 181 ° C. less than the ceiling temperature was added,
vi) neutralizing the particles so formed with a base to a pH value of at least 7.5 and subsequently vii) at least one nonionic ethylenically unsaturated monomer of 90-99.9% by weight and at least A process for producing emulsion polymer particles by making a multi-stage emulsion polymer by polymerizing with a third shell containing 0.1 to 10% by weight of one hydrophilic monoethylenically unsaturated monomer. Further, after the step vii), there is a step of polymerizing with another shell including viii) at least one nonionic ethylenically unsaturated monomer and at least one hydrophilic monoethylenically unsaturated monomer. The method of claim 1. The process according to claim 1 or 2 , characterized in that the mass ratio of expanded seed (ii) to seed polymer (i) is 2: 1 to 50: 1. The method according to any one of claims 1 to 3 , characterized in that the average particle size in the non-expanded state of the core stage polymer comprising the seed (i) and the expanded seed (ii) is 100 to 400 nm. The glass transition point measured according to the Fox equation of the core stage polymer, characterized in that the is between 0.99 ° C. from -20 ° C., any one process of claim 1 to 4. 6. Process according to any one of claims 1 to 5 , characterized in that the mass ratio of core stage polymer to first shell (iii) is 20: 1 to 1: 1. The method according to any one of claims 1 to 6 , characterized in that the shell polymer (iii) has a glass transition point measured according to the Fox equation between -60 ° C and 120 ° C. 8. A method according to any one of claims 1 to 7 , characterized in that the particle size of stage (iii) in the unexpanded state is 120 nm to 500 nm. The method according to any one of claims 1 to 8 , characterized in that the mass ratio of the first shell (iii) to the second shell (iv) is 1:30 to 1: 1. 10. Process according to any one of claims 1 to 9 , characterized in that the shell polymer (iv) has a glass transition point according to a Fox of 50-120 [deg.] C. The process according to any one of claims 1 to 10 , characterized in that the average particle size of step (iv) is 200-1500 nm. The plasticizer monomer described in (v) is α-methylstyrene, 2-phenylacrylic acid / atropic acid ester, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1,1- 12. Process according to any one of claims 1 to 11 , characterized in that it is selected from the group of diphenylethene or methyl-2-t-butyl acrylate. 13. Process according to claim 12 , characterized in that the ester of 2-phenylacrylic acid / atropic acid is an ester of methyl, ethyl, n-propyl or n-butyl. Bases described in (vi) is an alkali metal compound or alkaline earth metal compound or ammonia; and wherein the primary amine is a secondary amine or tertiary amine, Claims 1 to 13 The method of any one of these. An alkali metal compound or an alkaline earth metal compound is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide and sodium carbonate, a primary amine, a secondary amine or a tertiary amine is ethylamine, Propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethyl Ethanolamine, diisopropanolamine, morpholine, ethylenediamine, 2-diethylamineethylamine, 2,3-diaminopropane, 1,2-propylenediamine, dimethylaminopro Triethanolamine, neopentanediamine, hexamethylenediamine, 4,9-oxa-1,12-diamine, characterized in that it is selected from polyethylene imine and polyvinyl amine The method of claim 14, wherein. 16. The method according to any one of claims 1 to 15 , characterized in that the mass ratio of the third shell (viii) to the second shell (iv) is 5: 1 to 1: 2. 16. Process according to any one of claims 1 to 15 , characterized in that the shell polymer (vii) has a glass transition point according to a Fox of 50-120 [deg.] C. Use of polymer particles produced according to the method of any one of claims 1 to 16 in thermoplastic molding materials as impact modifiers in paints, paper coatings, cosmetics or foams.   An aqueous emulsion polymer comprising water and a multi-stage emulsion polymer obtained according to the method of claim 1.